Thermoplastic elastomeric resin composition and a process for the preparation thereof

ABSTRACT

The invention provides a process for the preparation of a thermoplastic elastomeric resin composition comprising (a) 100 parts by weight of a block copolymer consisting of at least two polymeric blocks (A) composed of a vinyl aromatic compound and at least one polymeric block (B) composed of a conjugated diene compound, or a hydrogenated block copolymer, (b) 20 to 300 parts by weight of a non-aromatic softening agent for rubber, (c) 1 to 100 parts by weight of a peroxide-crosslinking type olefinic resin or a copolymeric rubber containing said resin, and (d) 10 to 150 parts by weight of a peroxide-decomposition type olefinic resin or a copolymer containing said resin, characterized in that the process comprises a step of heat-processing component (a), component (b), at least a part of component (c) and a part of component (d) in the presence of an organic peroxide to cause crosslinking, and a subsequent step of blending these with the remaining part of component (d) and, if any, the remaining part of component (c). The obtained composition is soft and good in rubber properties, mechanical strength and processability, and is less sticky.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a divisional of U.S. patent application Ser. No.08/639,366, filed Apr. 26, 1996, now U.S. Pat. No. 5,929,165.

FIELD OF THE INVENTION

The present invention relates to a thermoplastic elastomeric resincomposition and a process for the preparation thereof.

PRIOR ART

Thermoplastic elastomeric resins which are rubber-like materials, do notneed a vulcanization process and have molding processability similar asthat of thermoplastic resins are attracting attention in the fields ofauto parts, parts for electric appliances, electric wire insulation,footwears and general goods.

Various types of such thermoplastic elastomeric resins have beendeveloped and put on sale, such as polyolefine type, polyurethane type,polyester type, polystyrene type and polyvinyl chloride type.

Among those, polystyrene type thermoplastic elastomeric resins such asstyrene-butadiene block copolymers (SBS) and styrene-isoprene blockcopolymers (SIS) have high softness and good rubber elasticity at normaltemperature. Further, thermoplastic elastomeric resin compositionsobtained from these show good processability.

However, these polymers have problems in resistance to weathering asthey have double bonds in conjugated diene blocks in molecule.

To overcome the problems, the double bonds in block copolymers ofstyrene and conjugated diene are hydrogenated to give elastomeric resinswith improved thermal stability.

Several thermoplastic elastomeric resin compositions of suchhydrogenated ones have be proposed, for instance, in Japanese PatentApplication Laid-Open (hereinafter refereed to as JP Laid-Open) Nos.50-14742/1975 and 52-26551/1977. As modification of these, JP Laid-OpenNos. 58-132032/1983, 58-145751/1983, 59-53548/1984, 59-131613/1984 and62-48757 disclose compositions comprising a hydrogenatedstyrene-conjugated diene block copolymer, a hydrocarbon and analpha-olefin polymeric resin, and a process for the preparation thereof.

Unfortunately, the thermoplastic elastomeric resin compositions of theprior art comprising such hydrogenated block copolymers have a drawbackin rubber properties, such as deformation under heat and pressure(compression set) and rubber elasticity at a high temperature.

To solve such a drawback, there have been proposed a cross-linkingcomposition in which a silane compound is added to a compositioncontaining such a hydrogenated block copolymer, and cross-linked oneobtained by cross-linking a composition containing such a hydrogenatedblock copolymer in the presence of an organic peroxide, for instance, inJP Laid-Open Nos. 59-6236/1984 and 62-57662/1987, Japanese PatentPublication Nos. 3-49927/1991, 3-11291/1991, 3-58381/1991 and6-13628/1994. Particularly, JP Laid-Open No. 59-6236/1984 discloses aprocess for the preparation of an elastomeric composition comprising (i)a hydrogenated block copolymer, (ii) a peroxide-crosslinking typeolefinic copolymer, (iii) a non-aromatic softening agent for rubber and(iv) a peroxide-decomposition type olefinic resin, wherein component(ii) and, optionally components (iii) and (iv), are heat treated in thepresence of an organic peroxide to cause crosslinking and, then,component (i) is blended with the partially cross-linked substances. Apart of component (iv) may be blended with the partially cross-linkedsubstances. However, component (i) is not subjected to the crosslinkingreaction.

However, such proposed cross-linked compositions of the hydrogenatedblock copolymer are unsatisfactory in compression set at a hightemperature, particularly at 100° C. and, further, do not meet thelevels of properties previously required in the fields of vulcanizedrubber. Particularly, good processability cannot be attained, and themechanical strength is low.

In addition, the proposed compositions have some other practicalproblems. For instance, the surface of a molded article from suchcompositions shows stickiness due to the decomposition of aperoxide-decomposition type polymer caused in blending with an organicperoxide.

Further, the proposed compositions are apparently more liable to bescratched than PVC or TPU. Accordingly, a lubricant is added in mostcases to lower a dynamic friction coefficient so as to improveresistance to scratch. Alternatively, the composition is coated with aultra-high molecular weight polyethylene or two-color molded to improvethe scratch resistance of the thermoplastic elastomer (JP Laid-Open Nos.5-4522/1993 and 7-40508/1995). However, those need special moldingtechnique and are less applicable for various purposes.

Alternatively, a ultra-high molecular weight polyethylene is blended toattain a sliding property (JP Laid-Open No. 1-313548/1989 and JPPublication 7-81042/1995). However, the thermoplastic elastomercompositions disclosed there have a narrow range of hardness, or are badin compression set at a high temperature and in resistance to oil.

Further, the proposed compositions mentioned above all have a Shore Ahardness of 40 or more. An increased amount of a softening agent hasbeen added to make the composition softer. Then, some problems arise inpractice, such as stickiness on the surface of a molded article orbleed-out of the softening agent under heat and stress.

JP Laid-Open No. 7-138418/1995 discloses an olefine-elastomercomposition comprising an ethylene-(meth)acrylate copolymer and anethylene-α-olefine copolymer or a hydrogenated block copolymerconsisting of at least one polymeric block (A) composed mainly of a vinyaromatic compound and at least one polymeric block (B) composed mainlyof a conjugated diene compound. JP Laid-Open No. 8-34900/1996 disclosesa composition comprising a hydrogenated block copolymer consisting of atleast two polymeric blocks (A) composed mainly of a viny aromaticcompound and at least one polymeric block (B) composed mainly ofisoprene, and an oil and, optionally, a polyolefine resin, wherein theoil may be an aromatic or non-aromatic softening agent for rubber.

SUMMARY OF THE INVENTION

A purpose of the invention is to provide a process for the preparationof a thermoplastic elastomeric resin composition which is soft and goodin rubber properties, mechanical strength and processability, and, isless sticky.

Another purpose of the invention is to provide a composition which showshigh resistance to oil and high resistance to scratch as well as theaforesaid properties and a process for the preparation thereof.

A further purpose of the invention is to provide a composition which isultra-soft and good in rubber properties, mechanical strength andprocessability, and is less sticky.

Thus, the invention provides a process for the preparation of athermoplastic elastomeric resin composition comprising

(a) 100 parts by weight of a block copolymer consisting of at least twopolymeric blocks (A) composed mainly of a viny aromatic compound and atleast one polymeric block (B) composed mainly of a conjugated dienecompound, or a hydrogenated block copolymer obtained by hydrogenatingsaid block copolymer,

(b) 20 to 300 parts by weight of a non-aromatic softening agent forrubber,

(c) 1 to 100 parts by weight of a peroxide-crosslinking type olefinicresin or a copolymeric rubber containing said resin, and

(d) 10 to 150 parts by weight of a peroxide-decompostion type olefinicresin or a copolymer containing said resin,

characterized in that the process comprises a step of heat-processingcomponent (a), component (b), at least a part of component (c) and apart of component (d) in the presence of an organic peroxide to causecrosslinking, and a subsequent step of blending these with the remainingpart of component (d) and, if any, the remaining part of component (c).

It is essential that component (a) is also subjected to theheat-processing in the presence of an organic peroxide, wherebycomponent (a) is partially cross-linked and better dispersion of all thecomponents is attained. The obtained composition is soft and good inrubber properties, mechanical strength and processability, and is lesssticky.

In a preferred embodiment, (e) 1 to 30 parts by weight of a polyestertype thermoplastic elastomer, (f) 0.5 to 10 parts by weight of asilicone having a weight average molecular weight of at least 70,000 or0.1 to 3 parts by weight of a compound having a perfluoroalkyl group,and (g) 1 to 20 parts by weight of a straight silicone oil having aweight average molecular weight of at most 50,000 are present in saidheat processing in the presence of an organic peroxide.

Then, the invention further provides a thermoplastic elastomeric resincomposition comprising

(a) 100 parts by weight of a block copolymer consisting of at least twopolymeric blocks (A) composed mainly of a viny aromatic compound and atleast one polymeric block (B) composed mainly of a conjugated dienecompound, or a hydrogenated block copolymer obtained by hydrogenatingsaid block copolymer,

(b) 20 to 300 parts by weight of a non-aromatic softening agent forrubber,

(c) 1 to 100 parts by weight of a peroxide-crosslinking type olefinicresin or a copolymeric rubber containing said resin, and

(d) 10 to 150 parts by weight of a peroxide-decompostion type olefinicresin or a copolymer containing said resin,

characterized in that the composition further comprises

(e) 1 to 30 parts by weight of a polyester type thermoplastic elastomer,

(f) 0.5 to 10 parts by weight of a silicone having a weight averagemolecular weight of at least 70,000 or 0.1 to 3 parts by weight of acompound having a perfluoroalkyl group, and

(g) 1 to 20 parts by weight of a straight silicone oil having a weightaverage molecular weight of at most 50,000.

This composition shows high resistance to oil and high resistance toscratch as well as teh properties mentioned above.

In another preferred embodiment of the process according to theinvention, the process comprises a step of heat-processing component(a), component (b), at least a part of component (c), at least a part ofcomponent (d) and 10 to 100 parts by weight of a hydrogenated petroleumresin in the presence of an organic peroxide to cause crosslinking, anda subsequent step of blending these with the remaining parts ofcomponents (c) and (d), if any.

Then, the invention further provides a thermoplastic elastomeric resincomposition comprising

(a) 100 parts by weight of a block copolymer consisting of at least twopolymeric blocks (A) composed mainly of a viny aromatic compound and atleast one polymeric block (B) composed mainly of a conjugated dienecompound, or a hydrogenated block copolymer obtained by hydrogenatingsaid block copolymer,

(b) 20 to 300 parts by weight of a non-aromatic softening agent forrubber,

(c) 1 to 100 parts by weight of a peroxide-crosslinking type olefinicresin or a copolymeric rubber containing said resin, and

(d) 10 to 150 parts by weight of a peroxide-decompostion type olefinicresin or a copolymer containing said resin,

characterized in that the composition further comprises

(h) 1 to 100 parts by weight of a hydrogenated petroleum resin.

The last composition is ultra-soft and good in rubber properties,mechanical strength and processability, as is less sticky.

PREFERRED EMBODIMENTS OF THE INVENTION Component (a), Block Copolymer

Component (a) used in the invention is a block copolymer consisting ofat least two polymeric blocks (A) composed mainly of a viny aromaticcompound and at least one polymeric block (B) composed mainly of aconjugated diene compound, or a hydrogenated block copolymer obtained byhydrogenating said block copolymer, or a mixture thereof, such as vinylaromatic compound-conjugated diene compound block copolymers having astructure, A-B-A, B-A-B-A or A-B-A-B-A, or those obtained byhydrogenating such. The block copolymer and/or the hydrogenated blockcopolymer (hereinafter referred to as (hydrogenated) block copolymer)contains 5 to 60% by weight, preferably 20 to 50% by weight, of a vinylaromatic compound. Preferably, the polymeric block A composed mainly ofa vinyl aromatic compound consists wholly of a vinyl aromatic compoundor is a copolymeric block comprising more than 50% by weight, preferablyat least 70% by weight, of a vinyl aromatic compound and a conjugateddiene compound and/or a hydrogenated conjugated diene compound(hereinafter referred to as (hydrogenated) conjugated diene compound).Preferably, the polymeric block B composed mainly of a (hydrogenated)conjugated diene compound is composed solely of a (hydrogenated)conjugated diene compound or is a copolymeric block comprising more than50% by weight, preferably at least 70% by weight, of a (hydrogenated)conjugated diene compound with a vinyl aromatic compound. The vinylcompound or the (hydrogenated) conjugated diene compound may bedistributed at random, in a tapered manner (i.e., a monomer contentincreases or decreases along a molecular chain), in a form of partialblock or mixture thereof in the polymeric block A composed mainly of avinyl aromatic compound or the polymeric block B composed mainly of a(hydrogenated) conjugated diene compound, respectively. When two or moreof the polymeric block A composed mainly of a vinyl aromatic compound ortwo or more of the polymeric block B composed mainly of a (hydrogenated)conjugated diene compound are present, they may be same with ordifferent from each other in structure.

The vinyl aromatic compound to compose the (hydrogenated) blockcopolymer may be one or more selected from, for instance, styrene,α-methyl styrene, vinyl toluene and p-tert.-butyl styrene, preferablystyrene. The conjugated diene compound may be one or more selected from,for instance, butadiene, isoprene, 1,3-pentadiene, and2,3-dimethyl-1,3-butadiene, preferably butadiene and/or isoprene.

Any microstructure may be selected in the polymeric block B composedmainly of the conjugated diene compound. It is preferred that thebutadiene block has 20 to 50%, more preferably 25 to 45%, of1,2-microstructure. In the polyisoprene block, it is preferred that 70to 100% by weight of isoprene is in 1,4-microstructure and at lest 90%of the aliphatic double bonds derived from isoprene is hydrogenated.

A weight average molecular weight of the (hydrogenated) block copolymerwith the aforesaid structure to be used in the invention is preferably5,000 to 1,500,000, more preferably 10,000 to 550,000, particularly10,000 to 400,000. A ratio of the weight average molecular weight (Mw)to the number average molecular weight (Mn), Mw/Mn, is preferably 10 orless, more preferably 5 or less, particularly 2 or less.

Molecule structure of the (hydrogenated) block copolymer may be linear,branched, radial or any combination thereof.

Many methods were proposed for the preparation of such block copolymers.As described, for instance, in JP Publication 40-23798/1965, blockpolymerization may be carried out using a lithium catalyst or a Zieglercatalyst in an inert solvent. The hydrogenated block copolymer may beobtained by hydrogenating the block copolymer thus obtained in thepresence of a hydrogenation catalyst in an inert solvent.

Examples of the (hydrogenated) block copolymer include SBS, SIS, SEBSand SEPS. A particularly preferred (hydrogenated) block copolymer in theinvention is a hydrogenated block copolymer with a weight averagemolecular weight of 50,000 to 550,000 which is composed of polymericblock A composed mainly of styrene and polymeric block B which iscomposed mainly of isoprene and in which 70 to 100% by weight ofisoprene has 1,4-microstructure and 90% of the aliphatic double bondsderived from isoprene is hydrogenated. More preferably, 90 to 100% byweight of isoprene has 1,4-microstructure in the aforesaid hydrogenatedblock copolymer.

Component (a) may be modified, for instance, by maleic anhydrides,epoxides or carboxylic acid.

Component (b), Non-Aromatic Softening Agent for Rubber

Non-aromatic mineral oils and non-aromatic liquid or low molecularweight synthetic softening agents may be used as component (b) of theinvention. Mineral oil softening agents used for rubber are mixtures ofaromatic cyclic ones, napththenic cyclic ones and paraffinic ones. Thosein which 50% or more of the whole carbon atoms is in paraffinic chainsare called a paraffinic type; those in which 30 to 40% of the wholecarbon atoms is in naphthenic rings are called a naphthenic type; andthose in which 30% or more of the whole carbon atoms is in aromaticrings are called an aromatic type.

Mineral oil softening agents for rubber to be used as component (b)according to the invention are the paraffinic type or the naphthenictype. The aromatic softening agents are improper, because they makecomponent (a) soluble and hinder the crosslinking reaction so thatphysical properties of a composition obtained are not improved.Paraffinic ones are preferred as component (b). Among the paraffinicones, those with a less content of aromatic cyclic components areparticularly preferred.

The non-aromatic softening agents for rubber have a kinetic viscosity at37.8° C. of 20 to 500 cSt, a pour point of -10 to -15° C. and a flashpoint (COC) of 170 to 300° C.

Component (b) is blended in an amount of 20 to 300 parts by weight,preferably 40 to 150 parts by weight, per 100 parts by weight ofcomponent (a). If it is used in an amount of more than 300 parts byweight, bleed-out of the softening agent tends to take place, a finalproduct might be sticky, and mechanical properties are worsened. If itis used in an amount of less than 20 parts by weight, processability ofthe composition is bad. A part of component (b) may be blended after theheat treatment in the presence of peroxide, which is however notpreferred as bleed-out might occur. Component (b) preferably has aweight average molecular weight of 100 to 2,000.

Component (c), Peroxide-Crosslinking Type Olefinic Resin or aCopolymeric Rubber Containing the Same

As component (c) of the invention, use may be made of those which mainlystarts cross-linking by being heat-treated in the presence of peroxideso that its flowability decreases, such as polyethylene having a polymerdensity of 0.88 to 0.94 g/cm³, for instance, high density polyethylene,low density polyethylene, linear low density polyethylene and ultra-lowdensity polyethylene, and amorphous random copolymeric elastomers suchas ethylene-propylene copolymeric rubber andehtylene-proplyrene-non-conjugated diene copolyemeric rubber. Amongthose, polyethylene and ethylene-propylene copolymeric rubber arepreferred. Particularly, linear low density polyethylene is suitable, asproper crosslinked structure is attained.

When component (c) is rubber, its Mooney viscosity, ML1+4 (100° C.), ispreferably 10 to 120, more preferably 40 to 100. If rubber with a Mooneyviscosity of less than 10 is used, rubber properties of an elastomercomposition obtained are worse. If rubber with a Mooney viscosity ofmore than 120, processability is worse and, particularly, appearance ofa molded article is worse.

An ethylene content in the copolymer is properly 5 to 50% by weight,preferably 6 to 20% by weight, more preferably 10 to 15% by weight. Ifthe ethylene content is less than 5% by weight, softness of an elastomercomposition obtained is insufficient. If it is larger than 50% byweight, mechanical strength is worse. The peroxide-crosslinking typeolefinic resin or the copolymer containing the same preferably has aweight average molecular weight of 50,000 to 1,000,000, more preferably70,000 to 500,000. If it is less than 50,000, rubber properties of anelastomer composition obtained are worse. If it exceeds 1,000,000,processability is worse and, particularly, appearance of a moldedarticle is worse.

Component (c) is blended in an amount of 1 to 100 party by weight,preferably 3 to 50 parts by weight, per 100 parts by weight of component(a). If the amount is less than 1 part by weight, mechanical propertiesof an elastomer composition obtained are worse. If it exceeds 100 partsby weight, softness and processability of an elastomer compositionobtained are worse.

Preferably, at least a half of the amount of component (c), particularlyat least 3 parts by weight of component component (c), is blended beforethe heat treatment in the presence of peroxide. The remaining parts areblended after the heat treatment, whereby various properties may beadjusted as will be discussed below.

Component (d), Peroxide-Decomposition Type Olefinic Resin or a CopolymerContaining the Same

Component (d) of the invention attains an effect of improving dispersionof the rubber in the composition obtained so as to improve appearance ofa molded article. Component (d) is blended in an amount of 10 to 150parts by weight, preferably 25 to 100 parts by weight, per 100 parts byweight of component (a). If the amount is less than 10 parts by weight,processability of an elastomer composition obtained is worse. If itexceeds 150 parts by weight, softness and rubber elasticity of anelastomer composition are worse.

A peroxide-decomposition type olefinic resin suitable as component (d)of the invention has Tm of 150 to 167° C. and ΔHm of 25 to 83 mJ/mg, asdetermined by DSC on its homopolymeric part. Crystalinity may beestimated from Tm and ΔHm. If Tm and ΔHm are out of the aforesaidranges, rubber elasticity at 100° C. or higher of an elastomercomposition obtained is not improved.

It is preferred to use two types of peroxdie-decomposition type olefinicresins in combination as will be described below.

Peroxide-decomposition type olefinic resins to be blended before thecrosslinking reaction are preferably high molecular weight propylenehomopolymers such as isotactic polypropylenes, and high molecular weightcopolymers of propylene with a smaller amount of other α-olefine such as1-butene, 1-hexene or 4-methyl-1-pentene. These resins preferably havean MFR (ASTM D-1238, Condition L, 230° C.) of 0.1 to 10 g/10 min., morepreferably 0.1 to 5 g/10 min., particularly 0.1 to 3 g/10 min.Peroxide-decomposition type olefinic resins to be blended after thecrosslinking reaction are preferably one or more of highly flowableblock or random propylene compolymers or propylene homopolymers, such asisotactic polypropylenes or copolymers of propylene with a smalleramount of other α-olefine such as 1-butene, 1-hexene or4-methyl-1-pentene. These resins preferably have an MFR of 5 to 200 g/10min., more preferably 8 to 150 g/10 min., particularly 10 to 100 g/10min.

If the MFR of the peroxide-decomposition type olefinic resin to beblended before the crosslinking reaction is less than 0.1 g/10 min.,processability of an elastomer composition obtained is worse. If itexceeds 10 g/10 min., rubber elasticity of an elastomer compositionobtained is worse.

If the MFR of the peroxide-decomposition type olefinic resin to beblended after the crosslinking reaction is less than 5 g/10 min.,processability of an elastomer composition obtained is worse. If itexceeds 200 g/10 min., rubber elasticity of a composition obtained isworse.

Component (d) is blended in an amount of 10 to 150 parts by weight,preferably 20 to 80 parts by weight, per 100 parts by weight ofcomponent (a). If the amount is less than 10 parts by weight,processability is worse. If it exceeds 150 parts by weight, an elastomercomposition obtained is too hard and lacks flexibility, so that it isdifficult to obtain an article with rubber-like touch.

According to the invention, a part of component (d), preferably at least3 parts by weight of component (d), is subjected to the heat treatmentin the presence of an organic peroxide, and the remaining part ofcomponent (d), preferably at least 5 parts by weight of (d), is blendedafter the heat treatment. All components are dispersed uniformly by suchportionwise addition of component (d), so that stickiness on the surfaceof a molded article disappears and processability is also improved.

It is preferred that the amount of component (d) to be blended beforethe crosslinking reaction (X) is less than that after the crosslinkingreaction (Y), because the resin composition will have better rubberproperties. The aforesaid X and Y may be determined depending upon afinal molding process, such as injection molding or extrusion molding,in a specific case.

Component (e), Polyester Type Thermoplastic Elastomer

As component (e) of the invention, use may be made of those which do notcause crosslinking in the heat treatment in the presence of peroxideand, therefore, their flowabilities do not decrease, such aspolyetherester block copolymers composed of polybutylene terephthalateas a main hard segment and poly(tetramethyleneoxide)glycol as a softsegment, and polyesterester block copolymers composed of polybutyleneterephthalate as a main hard segment and poly-ε-caprolactam or otherpolyesters as a soft segment. Component (e) is blended in an amount of130 parts by weight or less, preferably 10 to 60 parts by weight orless, more preferably 10 to 60 parts by weight, per 100 parts by weightof component (a). If the amount exceeds 130 parts by weight, softness ofan elastomer composition obtained is low and processability is worse. Ina preferred embodiment of the invention where (f) silicone or a compoundhaving a perfluoroalkyl group and (g) straight silicone oil are furtherblended, component (e) is used in an amount of 1 to 30 parts by weight,preferably 3 to 20 parts by weight, per 100 parts by weight of component(a). If the amount exceeds 30 parts by weight, softness of an elastomercomposition obtained and processability are worse. Component (e)preferably has Tm of 160 to 225° C., a D hardness of 30 or more and ahard segment content of 30 to 80%, more preferably a hard segmentcontent of 50 to 80%. Resistance to oil and resistance to heat of theelastomer composition are enhanced by the incorporation of component(e). The resistance to heat used herein refers to temperaturedependencies of compression set and hardness.

Component (f), Silicone or a Compound Having a Perfluoalkyl Group

Silicone as component (f) has a weight average molecular weight of atleast 70,000, preferably at least 100,000. There is no particular upperlimit on the molecular weight, but it is preferably one million. Thesilicone may be dimethyl, methylphenyl or methylhydrogen polysiloxane ormodified silicone, but not limited to these. The silicone improvesprocessability and molding operability of the composition, and, further,improves surface lubricity and surface gloss of a molded article. Foreasier handling, the silicone may be compounded with a thermoplasticresin such as polyethylene, polypropylene or polystyrene at a highconcentration, e.g., 30 to 70% by weight, A compound with polyethyleneis particularly superior in the effects.

The silicone is blended in an amount of 0.5 to 10 parts by weight,preferably 1.5 to 5 parts by weight, per 100 parts by weight ofcomponent (a). Even if the amount exceed 10 parts by weight, furtherimprovement is little and, rather, stickiness occurs.

Examples of the compound having a perfluoroalkyl group includeperfluoroalkyl sulfonic acid salts, perfluoroaklyl carbonic acid salts,perfluoroalkyl ethyleneoxide adducts, perfluoroalkyl group-containingolefinic oligomers with the last one being preferred. When it is apolymer or oligomer, it preferably has a weight average molecular weightof 2,000 to 20,000, more preferably 5,000 to 10,000.

The compound having a perfluoroalkyl group is blended in an amount of0.1 to 3 parts by weight, preferably 0.1 to 1.5 parts by weight. Thecompound having a perfluoroalkyl group may be used together with theaforesaid silicone.

Component (g), Straight Silicon Oil

Component (g), straight silicone oil, has a molecular weight lower thanthat of the silicone as component (f), and thus has a weight averagemolecular weight of 5,000 to 50,000, preferably 10,000 to 20,000. Usemay be made of dimethyl silicone oils, methylphenyl silicone oils,methylhydrogne silicone oils or modified silicone oils having otherorganic groups. It its molecular weight is less than 5,000, bleed-out isconspicuous. Regarding a viscosity, those having a viscosity of 100 to1,000 cSt are proper. The straight silicone oil improves surfacelubricity of a molded article.

The straight silicone oil is blended in an amount of 1 to 20 parts byweight, preferably 3 to 10 parts by weight, per 100 parts by weight ofcomponent (a). Even if the amount exceeds 20 parts by weight, furtherimprovement is little and, rather, bleed-out becomes conspicuous.

Hydrogenated Petroleum Resin

A hydrogenated petroleum resin may be blended in the invention, ifneeded. Examples of the hydrogenated petroleum resin includehydrogenated aliphatic petroleum resins, hydrogenated aromatic petroleumresins, hydrogenated copolymer petroleum resins, hydrogenated alicyclicpetroleum resins and hydrogenated terpene resins.

The hydrognated petroleum resins may be obtained by hydrogenating, in aconventional manner, petroleum resins produced in conventionalprocesses.

The petroleum resin used herein refers to resineous substances obtainedin various processes in the refining industry and the petrochemicalindustry, or resins obtained by copolymerizing unsaturated hydrocarbonsrecovered from such processes, particularly from a naphtha crackingprocess, for instance, aromatic petroleum resins composed mainly of a C₅fraction, aromatic petroleum resins composed mainly of a C₉ fraction,copolymeric petroleum resins from those, and alicyclic petroleum resins.

A preferred hydrogenated petroleum resin is of hydrogenated resin type,particularly, such obtained by copolymerizing cyclopentadiene typecompounds with vinyl aromatic compounds and hydrogenating the copolymerobtained.

The hydrogenated petroleum resin used in the invention is preferably onewhich is completely hydrogenated. Partially hydrogenated ones tend to beworse in stability and resistance to weathering.

The hydrogenated petroleum resin is blended in an amount of 100 parts byweight or less, preferably 10 to 100 parts by weight or less, morepreferably 10 to 80 parts by weight, per 100 parts by weight ofcomponent (a). Even if the amount exceeds 100 parts by weight, a furthersoftening effect on an composition obtained is little and, rather, anaction of the petroleum resin as a tackifier becomes conspicuous andmechanical properties become worse as well. If the amount is less than10 parts by weight, no softening effect on a composition obtained isrecognized. If a non-hydrogenated petroleum resin is used, heatstability of a composition obtained is bad, so that the purpose of theinvention is not attained.

Inorganic Filler

Inorganic fillers may be blended, if needed. The fillers improve somephysical properties, such as a permanent compressive strain of a moldedarticle, and further offer an economical advantage as an extender. Anyconventional inorganic fillers may be used, such as calcium carbonate,talc, magnesicum hydroxide, mica, clay, barium sulfate, natural silica,synthetic silica (white carbon), titanium oxide, and carbon black. Amongthose, calcium carbonate and talc are particularly preferred.

The inorganic filler may be blended in an mount of 0 to 100 parts byweight, preferably 0 to 60 parts by weight, per 100 parts by weight ofcomponent (a). If the amount exceeds 100 parts by weight, mechanicalstrength of an elastomer composition obtained is very low and, further,its hardness is so high that its flexibility is lost and an article withrubber-like touch cannot be obtained.

Electron Doner

Electron doners may be blended. The electron doner used herein means onewhich has, in its structure, an atom, ion or moiety liable to give anelectron to others. There may be named aromatic hydrocarbons such asbenzene and naphthalene or substitution derivatives thereof, amines,carboxylic acids, carboxylic aid anhydrides, carboxylic acid esters,alcohols, ethers, ketones, aldehydes, and alcoholates. Examples of theelectron-donating atoms or ions include a chloride ion, fluoride ion andiodide ion. Examples of the electron-donating group include an aminogroup, an imino group, a hydroxyl group, a halogen group, an alkyl groupand an allyl group. Examples of the electron-donating monomer includeethyleneimine.

Examples of the aromatic hydrocarbons include benzene, toluene,o-xylene, m-xylene, p-xylene, pseudcumene, isodurene, durene,pentamethyl benzene, hexamethyl benzene, ethyl benzene, propyl benzene,styrene, cumene, mesitylene, cymene, biphenyl, naphthalene, anthracene,indene, phenanthrene, indane, p-terphenyl, diphenylmethane,triphenylmethane, bibenzyl, stilbene and tetralin.

Examples of the carboxylic acids include aliphatic monocarboxylic acidssuch as formic acid, acetic acid, propionic acid, butyric acid,isobutyric acid, valeric acid, capric acid, pivalic acid, acrylic acid,methacrylic acid and crotonic acid; aliphatic dicarboxylic acids such asmalonic acid, succinic acid, glutaric acid, adipic acid, sebacic acid,maleic acid and fumaric acid; alicyclic carboxylic acids such ascyclohexanemonocarboxylic acid, cyclohexenemonocarboxylic acid,cis-1,2-cyclohexanedicaboxylic acid, andcis-4-methylcyclohexene-1,2-dicarboxylic acid; aromatic monocarboxylicacids such as benzoic acid, toluic acid, anisic acid, p-tert.-butylbezoic acid, naphthoic acid and cinnamic acid; and aromaticpolycarboxylic acids such as phthalic acid, isophthalic acid,terephthalic acid, naphthalic acid, trimellitic acid, hemimellitic acid,trimesic acid, pyromellitic acid and mellitic acid.

As the carboxylic acid anhydrides, use may be made of anhydrides of theaforesaid carboxylic acids.

As the carboxylic acid ester, use may be made of mono- or polyester ofthe aforesaid carboxylic acids, such as butyl formate, ethyl acetate,butyl acetate, isobutyl isobutyrate, propyl pivalate, isobutyl pivalate,ethyl acrylate, ethyl methacrylate, isobutyl methacrylate, diethylmalonate, diisobutyl malonate, dibutyl succinate, diethyl succinate,diethyl glutarate, dibutyl glutarate, diisobutyl glutarate, diisobutyladipate, dibutyl maleate, diisobutyl maleate, dibutyl sebacate, diethylsebacate, monomethyl maleate, diethyl tartrate, dibutyl tartrate,diisobutyl tartrate, ethyl cyclohexanecarboxylate, methyl benzoate,ethyl benzoate, methyl p-toluylate, ethyl p-tert.-butylbenzoate, ethylp-anisate, ethyl α-naphthoate, isobutyl α-naphthoate, ethyl cinnamate,monomethyl phthalate, monobutyl phthalate, dibutyl phthalate, diisobutylphthalate, dihexyl phthalate, dioctyl phthalate, di-2-ethylhexylphthalate, diallyl phthalate, diphenyl phthalate, diethyl isophthalate,dibutyl isophthalate, dibutyl terephthalate, diethyl naphthalate,dibutyl naphthalate, triethyl trimellitate, butyl trimellitate,tetramethyl pyromellitate, tetraethyl pyromellitate and tetrabutylpyromellitate.

As the carboxylic acid halides, use may be made of halides of theaforesaid caroxylic acids, such as acetyl chloride, acetyl bromide,acetyl iodide, propionyl chloride, butyryl chloride, butyryl bromide,butyryl iodide, pivalyl chloride, pivalyl bromide, acrylyl chloride,acrylyl bromide, acrylyl iodide, methacrylyl iodide, crotonyl chloride,malonyl chloride, succinyl bromide, glutaryl chloride, glutaryl bromide,adipoyl chloride, adipoyl bromide, sebacoyl chloride, sebacoyl bromide,maleoyl chloride, maleoyl bromide, fumaroyl chloride, fumaroyl bromide,tartaroyl chloride, cyclohexanecarboxyloyl chloride,1-cyclohexenecarboxyl chloride, cis-4-methylcyclohexenecarboxyloylchloride, cis-4-methylcyclohexenecarboxyloyl bromide, benzoyl chloride,benzoyl bromide, p-toluoyl chloride, p-toluoyl bromide, p-anisoylchloride, p-anisoyl bromide, α-naphthoyl chloride, cinnamoyl chloride,cinnamoyl bromide, phthaloyl dichloride, phthaloyl dibromide,isophthaloyl dichloride, isophthaloyl dibromide, terephthaloyldichloride, and naphthaloyl dichloride. Also, use may be made ofmonoalkyl hlides of dicarboxylic acids, such as methyl chloroformyladipate, ethyl chloroformyl maleate, methyl chloroformyl maleate andbutyl chloroformyl phthalate.

The alcohols may be represented by the general formula: ROH, wherein Ris, for instance, an alkyl, alkenyl, cycloalkyl, aryl or aralkyl grouphaving 1 to 12 carbon atoms. There may be named methanol, ethanol,propanol, isopropanol, butanol, pentanol, hexanol, octanol,2-ethylhexanol, cyclohexanol, benzyl alcohol, allyl alcohol, phenol,crezol, xylenol, ethylphenol, isopropylphenol, p-tert.-butylphenol, andn-octylphenol.

The ethers may be represented by the general formula: ROR', wherein Rand R' are, for instance, an alkyl, alkenyl, cycloalkyl, aryl or aralkylgroup having 1-12 carbon atoms. R and R' may be same with or differentfrom each other. R and R' may form a ring together. Examples of theethers include diethyl ether, diisopropyl ether, dibutyl ether,diisoamyl ether, di-2-ethylhexyl ether, diallyl ether, ethyl allylether, diallyl ether, diphenyl ether, arrisol and ethyl phenyl ether.Also, use may be made of cyclic ethers such as tetrahydrofuran, pyranand dioxane; linear ethers such as dimethoxyethane, diethyleneglycoldimethylether and triethyleneglycol dimethylether; cyclic vinyl etherssuch as 2,3-dihydrofuran, and 3,4-dihydro-2H-pyran; vinyl ethers such asmethyl vinyl ether and ethyl vinyl ether; cyclic allyl ethers such as2,5-dihydrofuran and 5,6-dihydro-2H-pyran; aliphatic amines such astriethylamine and triethylenediamine; aromatic amines such as pyridineand picoline; and heterocyclic compounds such as 2-oxazoline and6H-1,2,4-oxadiazine.

In the invention, preferred are toluene and methanol, particularlytoluene, as the electron doner.

The incorporation of the electron doner according to the invention hasan effect of decreasing the formation of cross-link gel in thethermoplastic elastomer composition produced. That is, it is believedthat the electron doner moderates a rate of crosslinking to attain theaforesaid effect. The amount of the electron doner used in the inventionmay vary depending upon the electron-donating ability of a particularelectron doner used, but may generally be 15 parts by weight or less,preferably 0.5 to 6 parts by weight, more preferably 2 to 3 parts byweight, per 100 parts by weight of component (a) in the case where it isblended before or during the heat treatment in the presence of peroxide.However, the amount may generally be 25 parts by weight or less,preferably 1 to 10 parts by weight, per 100 parts by weight of component(a), if the electron doner is previously mixed (e.g., kneaded) underheat with components (a) through (d) and others. If the electron doneris added in excess of the aforesaid upper limit, a molded article isgenerally sticky. However, the electron doners with lesselectron-donating ability may be added in excess of 15 parts by weight.The electron-donating ability is represented by a chain transferconstant of a polymer radical in the use of the electron doner. Thechain transfer constant varies with polymer types or reactiontemperatures, but the chain transfer constant of a styrene polymerradical at 60° C. (C_(S)) in the use of the electron doner is preferably10⁻⁴ to 10⁻⁶. When toluene is used as the electron doner, the chaintransfer constant of a styrene polymer radical is 1.25×10⁻⁵.

Organic Peroxide

Examples of the organic peroxides used in the invention include dicumylperoxide, di-tert.-butyl peroxide,2,5-dimethyl-2,5-di(tert.-butylperoxy) hexane,2,5-dimethyl-2,5-di(tert.-butylperoxy) hexine-3,1,3-bis(tert.-butylperoxyisopropyl) benzene,1,1-bis(tert.-butylperoxy)-3,3,5-trimethylcyclohexane,n-butyl-4,4,-bis(tert.-butylperoxy)valerate, benzoylperoxide,p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide,tert.-butylperoxy benzoate, tert.-butylperoxyisopropyl carbonate,diacetyl peroxide, lauroyl peroxide, and tert.-butylcumyl peroxide.

Among those, most preferred are2,5-dimethyl-2,5-di(tert.-butylperoxy)hexane and2,5-dimethyl-2,5-di(tert.-butylperoxy) hexine-3 in terms of smell,coloring and scorch stability.

The amount of the peroxide added is preferably 0.1 to 3 parts by weight,more preferably 0.5 to 2.5 parts by weight, particularly 0.8 to 2.5parts by weight, per total 100 parts by weight of components (a) to (e)present at the time of addition of the peroxide.

Crosslinking Auxiliary

In the partial crosslinking treatment in the presence of the organicperoxide in the process for the preparation of a thermoplastic elastomercomposition according to the invention, a crosslinking auxiliary may beblended, such as polyvalent vinyl monomers such as divinylbenzene andtriallycyanurate, and polyvalnet methacrylate monomers such asethyleneglycol dimethacrylate, diethyleneglycol dimethacrylate,triethylenglycol dimethacrylate, polyethylenglycol dimethacrylate,trimethylolpropane trimethacrylate and allyl methacrylate. Thesecompounds will cause the crosslinking reaction more uniformly and moreefficiently.

Triethylenegloycol dimethacrylate is most preferred, because thiscompound is easy to handle and well compatible with a main component tobe treated, peroxide-crosslinking type olefinic polymer rubber (c), andthis has a solubilizing action for the peroxide to act as a dispersionaid for the peroxide, so that the crosslinking action in the heattreatment is uniform and efficient to give a cross-linked thermoplasticelastomer with a good balance between hardness and rubber elasticity. Inaddition, triethyleneglycol dimethacrylate is well compatible with thepolyester type thermoplastic elastomer, so that surface peeling of amolded article is prevented.

The amount of the crosslinking auxiliary used in the invention ispreferably 0.1 to 10 parts by weight, more preferably 1 to 8 parts byweight, particularly 2 to 6 parts by weight, per total 100 parts byweight of components (a) to (e) present at the time of the addition ofthe crosslinking auxiliary. It is preferred that the amount of thecrosslinking auxiliary added is about 2 to 2.5 times as large as theamount of the peroxide added.

Antioxidant

Autioxidant may also be added, if needed, such as phenolic antioxidantsuch as 2,6-di-tert.-butyl-p-cresol, 2,6-di-tert.-butylphenol,2,4-di-methyl-6-tert.-butylphenol, 4,4-dihydroxydiphenyl, andtris(2-methyl-4-hydroxy-5-tert.-butylphenyl)butane, phosphite typeantioxidants and thioether type antioxidants. Among those, the phenolicantioxidants and the phosphate type antioxidants are preferred.

The amount of the antioxidant is preferably 3 parts by weight or less,more preferably 1 part by weight or less, per total 100 parts by weightof components (a) to (e) present at the time of the addition of theantioxidant. It is preferred to add the antioxidant in a first step ofthe preparation process mentioned below, so as to prevent hydrolysis ofthe polyester type thermoplastic elastomer.

The blend ratios among components (a) to (g), the electron doner and thecrosslinking auxiliary may actually be determined particularly inconsideration of a cross-link degree which affects the quality of athermoplastic elastomer composition obtained.

Process for the Preparation

The heat processing in the presence of an organic peroxide and theblending in the process for the preparation of the resin compositionaccording to the invention may be carried out by any conventional means.The process of the invention may be carried out, for instance, in thefollowing three steps.

In a first step, component (a), component (b), at least a part ofcomponent (c), and a part of component (d) are previously melt andkneaded together with optional additives such as an antioxidant, a lightstabilizer, a colorant and a flame retardant. Any conventional means forkneading rubbers or plastics may be used satisfactorily, such as singlescrew extruders, twin screws extruders, rolls, Banbury mixers, andvarious kneaders. In this step, a composition is obtained in which allof those components are dispersed uniformly.

In a second step, a peroxide and optionally a crosslinking auxiliary areadded to the composition obtained in the first step, and further kneadedunder heating to cause crosslinking. Particularly good properties areattained in this way, i.e., by previously kneading components (a) to (d)to have microdispersion and then adding an organic peroxide to causecrosslinking. This step may be carried out, for instance, by twin screwsextruders or Banbury mixers.

In a third step, the remaining part of component (d) and, if any, theremaining part of component (c) are added and kneaded. The kneading maybe carried out, for instance, by single screw extruders, twin screwsextruders, rolls, Banbury mixers, or various kneaders. In this step,dispersion of each component proceeds further and, at the same time, thereaction is completed.

A twin screws extruder with a L/D ratio of 47 or more or a Banbury mixeris preferred as a kneading means, because all of the steps may becarried out continuously. For instance, when a twin screws extruder isoperated with a screw rotation speed of 80 to 250 rpm, preferably 80 to100 rpm, each component is dispersed well to give good properties.

A kneading temperature in the first step is preferably set so that eachcomponent melts completely to become easy to mix. A kneading temperaturein the second step is preferably chosen so that a sufficient shearingforce acts on the organic peroxide and the other components and,further, the reaction proceeds uniformly. In the third step, thetemperature is desirably set so that the mixing of all of the componentsproceeds further and the reaction is completed.

Component (a) shall be added in the first step or, at latest, in thesecond step, whereby a part of component (a) causes a crosslinkingreaction to better the dispersion of each components. The resincomposition obtained according to the invention has an improvedresistance to heat as seen in the following Examples, unlike in JPLaid-Open 59-6236/1984.

Component (b) is preferably blended in the first step. If it is blendedin the third step, it will be a cause for bleed-out.

Component (c) may be blended all in the first step. However, a properamount of it may be blended in the first step and the remaining part ofit may be blended in the third step to adjust the processability,flowability and mechanical strength. The latter case is preferred,because the remaining part of component (c) added in the third step iscompatible with components (a) and (c) which were partially cross-linkedin the presence of a peroxide and comes into microdispersion, so thatphysical properties of the elastomer composition obtained, such asmechanical strength, are improved.

As mentioned above, a proper part of component (d) is blended in thefirst step and the remaining part is blended in the third step, wherebythe remaining part of component (d) added in the third step iscompatible with the composition which was partially cross-linked in thepresence of a peroxide and comes into microdispersion, so that physicalproperties of the elastomer composition obtained, such asprocessability, flowability and mechanical strength, are improved.

Component (e) is blended when higher resistances to heat and oil arerequested for the elastomer composition. Component (e) may be added inany step. However, it is preferred that a part of component (e) isblended in the third step to attain high resistances to heat and oil.For better compatibility, component (e) is added in the first step or,more preferably in the second step.

The inorganic filler may be blended in either step.

The electron doner may be blended in either one or both of the firststep and the second step. It is preferably blended in the second step togive better play to its function and to attain better efficiency. Whenthe electrondoner is blended in the first step, it might volatize duringthe kneading. Therefore, it is recommended to add to its amount,compared to the case where it is blended in the second step.

When component (e), polyester type elastomer, component (f), silicone ora perfluoroalkyl compound, and component (g), straight silicone oil, areall used in a composition, these may be blended in the first or secondstep.

A degree of the crosslinking of the thermoplastic elastomer compositionthus obtained is represented by a gel ratio and a dynamic elasticity.The gel ratio is determined as follows: 1 g of a sample is wrapped witha 100 mesh wire netting and extracted in boiling xylene in a Soxhletextractor for 10 hours. A ratio of the weight of the remaining solid tothe weight of the sample is the gel ratio. The dynamic elasticity isrepresented by a storage elasticity of melt viscoelasticity determinedby parallel plates.

In the invention, the degree of the crosslinking is preferably suchrepresented by a gel ratio of 30 to 45% by weight, more preferably 40 to45% by weight, and a storage elasticity of 105 to 107 Pa. Below theseranges, a compression set and resistance to oil of a thermoplasticelastomer composition obtained are bad. Above these ranges,processability is and bad, also, tensile properties deteriorate.

Each component is micro-dispersed more uniformly in the thermoplasticelastomer composition thus obtained, compared to compositions of theprior art. Accordingly, compression set, tensile strength and otherphysical properties are steadily attained.

The invention will be explained further in detail with reference to thefollowing Examples, but the invention shall not be limited to theExamples.

EXAMPLES Evaluation

Evaluations in the Examples and the Comparative Examples were made asfollows:

Hardness: Determined on the basis of the Japanese Industrial Standards(JIS) K 6301 and JIS S 6050 with a 6.3 mm thick press sheet as a sample.

Tensile strength: determined on the basis of JIS K 6301. A 1 mm thickpress sheet was punched out by no. 3 dumbbell. The tensile speed was 500mm/min.

Tensile elongation: determined on the basis of JIS K 6301. A 1 mm thickpress sheet was punched out by no. 3 dumbbell. The tensile speed was 500mm/min.

Stress at 100% elongation: determined on the basis of JIS K 6301. A 1 mmthick press sheet was punched out by no. 3 dumbbell. The tensile speedwas 500 mm/min.

Permanent set at 100% elongation: determined on the basis of JIS K 6301.A 1 mm thick press sheet was punched out by no. 3 dumbbell. The tensilespeed was 500 mm/min. After the sample was elongated by 100%, it washeld for 10 minutes, and then clamps were loosened. The sample was leftfree for 10 minutes. Then, the length between the bench marks wasmeasured.

Impact resilience: determined on the basis of BS 903 with a 4 mm thickpress sheet as a sample.

Compression set: determined on the basis of JIS K 6262 with a 6.3 mmthick press sheet as a sample. Conditions: 25% deformation; 70° C.×22hrs., 100° C.×22 hrs., 120° C.×22 hrs., and 140° C.×22 hrs.

Taper abrasion: based on JIS K 7204 with a 3 mm thick press sheet.Weight loss by abrasion was determined after 1,000 turns.

Spiral flow: a composition was injection molded with a 1 mm thick moldfor spiral flow test at a resin temperature of 220° C. and an injectionpressure of 800 kg/cm². A flow length of the composition was measured.

Dynamic friction coefficient and load to scratch: surface scratching wasconducted on a 1 mm thick press sheet using a HEIDON type surfaceproperty measuring device, Shintoh Kagaku Co., Type 14 DR. A load withwhich scratch was recognized (critical load) and a dynamic frictioncoefficient with a 200 g load were determined. Relative speed, 100mm/min.; scratching material, sapphire needle (point, 50 μm diameter, 90R) ; load, 0 to 600 g.

Tensile strength: based on JIS K 6301. A 2.5 mm thick press sheet waspunched out by dumbbell B. Tensile speed was 500 mm/min.

Resistance to oil: based on JIS K 6301. A 1 mm thick press sheet waspunched out by No. 3 dumbbell. ASTM No. 2 oil was used. Weight change,volume change, residual tensile strength and stress at 100% elongationwere measured after 70° C.×24 hrs. in Examples 1 to 30, ComparativeExamples 1 to 17, Examples 39 to 53 and Comparative Examples 30 to 41;or 120° C.×24 hrs. in Examples 31 to 38 and Comparative Examples 18 to29.

Processability: a composition was molded into a sheet of 8.5 mm×5 mm×3mm by a 80 tons injection molding machine in Examples 1 to 30Comparative Examples 1 to 17, Examples 39 to 53 and Comparative Examples30 to 41; or a sheet of 12.5 mm×13.5 mm×1 mm by a 120 tons injectionmolding machine in Examples 31 to 38 and Comparative Examples 18 to 29.Processability was evaluated as good when neither delamination nordeformation was recognized and no flow mark which would make appearancevery bad appeared.

Stickiness: evaluated as good when, on the molded sheet mentionedimmediately above, neither bleeding nor blooming of low molecular weightsubstances was recognized and no stickiness was felt in touch byfingers.

Cross-link gel: a belt of a 20 mm width and a 0.5 mm thickness wasextruded by a laboplastomill (Tohyo Seiki Co.) at 220° C. The number ofgels which were 0.5 mm² or larger according to a diagram for determiningcontaminants (Printing Bureau, the Ministry of Finance of Japan) werecounted in the belt of 20 m length by the naked eye and rated asfollows:

⊚: no cross-link gel (zero),

◯: 1 to 5 cross-link gels,

Δ: 6 to 10 cross-link gels, and

×: many (more than 11) cross-link gels.

Bleed-out: The molded sheet mentioned for the evaluation ofprocessability was compressed by 50% and stored at 100° C. for 22 hoursand then released. When neither beeding nor blooming of low molecularweight substances was recognized and no stickiness was felt in tough byfingers, the sheet was rated as ⊚.

Materials Used

Component (a): hydrogenated block copolymer, Septon 4055 (Kraray Co.)

styren content, 30% by weight; isoprene content, 70% by weight; weightaverage molecular weight, 130,000; molecular weight distribution(Mw/Mn), 1.3; and hydrogenation ratio, 90% or more.

Component (b): non-aromatic softening agent for rubber, Diana ProcessOil PW-90, (Idemitsu Kosan Co.), paraffin type oil, weight averagemolecular weight, 540; and content of aromatic components, 0.1% or less.

Component (c): peroxide-crosslinking type olefinic resin

PE-1, Idemitsu Petrochemical Co., V-0398CN (LLDPE, weight averagemolecular weight 80,000)

EP-1, Japan Synthetic Rubber Co., EP 961SP (EPR, weight averagemolecular weight 150,000)

Component (d): peroxide-decomposition type olefinic resin

PP-1, Asahi Kasei Co., E 1100 (PP, MFR 0.5 g/10 min.)

PP-2, low crystalline PP with Tm of 160° C., ΔHm of 45 mJ/mg, and MFR of2.5 g/10 min.

PP-3, Mitsubishi Petrochemical Co., BC03B (PP, MFR, 30 g/10 min.)

Component (e): polyester type thermoplastic elastomer, Teijin Co.,ELA4110N (ester-ester type)

Inorganic filler: calcium carbonate, Sankyo Seifun Co., RS400

Electron doner: toluene or methanol, Kanto Chemical Co., special grade

Peroxide: 2.5-dimethyl-2.5-di(tert.-butylperoxy)hexane, Nippon Oil &Fats Co., Perhexa 25B

Crosslinking anxiliary: triethyleneglycol dimethacrylate, ShinnakamuraKagaku Co., NK Ester 3G

Antioxidant: Asahidenka Co., PEP-36.

Examples 1 to 9

A resin composition was prepared in three steps as mentioned above. Thethree steps were consecutively conducted in a twin screws kneader with ascrew rotation of 100 rpm. The materials for the second and third stepswere fed via first and second intermediate feeders, respectively. Thetemperatures in each step are as follows:

first step, 230-240° C.,

second step, 180-220° C., and

third step, 200-220° C.

In the first step, components (a) , (b) , (c) , and PP-1 or PP-2 as apart of component (d) were fed together with the optional component (e),the inorganic filler, the electron doner and the anti-oxidant.

In the second step, the peroxide and the crosslinking auxiliary werefed.

The remaining part of component (d), i.e., PP-3, was fed in the thirdstep.

The amounts of the materials used are shown in weight part in Table 1.The results are as shown in Table 2.

                                      TABLE 1                                     __________________________________________________________________________    Example   1  2  3  4  5  6  7  8  9                                           __________________________________________________________________________    Component (a)                                                                           100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100                                           Component (b) 104 104 104 104 104 104 104 104. 104                            Component (c)                                                                 PE-1 4.2 4.2 14.6 19.8 25 4.2 4.2 4.2 4.2                                     EP-1      5.2 15.6  5.2                                                       Component (d)                                                                 PP-1  10.4 16 16 21 10.4 16 10.4 10.4                                         PP-2 21                                                                       PP-3 10.4 10.4 21 31 42 21 42 10.4 21                                         Component (e)      31 31 63 31                                                Inorganic filler 31 31 31 31 31 31 31 31                                      Peroxide 2.1 2.1 2.1 2.1 2.1 2.1 2.1 2.1 2.1                                  Cross-link auxiliary 4.7 4.7 4.7 4.7 4.7 4.7 4.7 4.7 4.7                      Anti-oxidant 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2                            __________________________________________________________________________

                                      TABLE 2                                     __________________________________________________________________________    Example         1  2  3  4  5  6  7  8  9                                     __________________________________________________________________________    Hardness, HDA, 15 sec. after                                                                  41 50 62 70 79 52 71 52 50                                      Tensile strength, kg/mm.sup.2 0.6 0.75 0.92 1.1 1.42 0.78 1.15 0.8 0.85       Tensile elongation, % 730 740 700 670 630 710 650 690 760                     Stress at 100% elongation, kg/mm.sup.2 0.25 0.35 0.47 0.62 0.72 0.37                                                0.52 0.38 0.35                          Permanent set at 100% elongation, % 3 3 3 5 7 3 5 3 3                         Impact resilience, % 68 63 58 55 53 60 53 63 63                               Compression set at 70° C. 26 28 30 33 37 31 35 28 30                   Compression set at 100° C. 29 30 34 36 42 33 38 30 32                  Compression set at 120° C. 30 31 34 35 44 35 41 30 33                  Compression set at 140° C. 32 34 36 40 49 38 44 36 35                  Taper abrasion, mg/1,000 turns 240 240 220 200 180 240 210 180 220                                                   Spiral flow 80 100 105 120 140                                               118 135 -- 125                          Tear strength, kg/mm 35 43 50 55 65 44 52 45 48                               Resistance to oil                                                             Residual tensile strength, % 85 86 86 89 90 92 95 93 90                       Stress at 100% elongation, kg/mm.sup.2 0.19 0.3 0.43 0.55 0.68 0.34                                                 0.59 0.34 0.34                          Weight change, % 38 35 30 27 20 38 30 25 40                                   Volume change, % 35 30 24 19 14 33 20 21 32                                   Gel ratio, % 45 44 42 40 38 -- -- -- --                                       Processability good good good good good good good good good                   Stickiness good good good good good good good good good                     __________________________________________________________________________

Examples 10 to 16

Compositions were prepared using the materials indicated in Table 3 in asimilar manner as in Example 1. The antioxidant was fed in the secondstep. In Examples 13, 14 and 15, 21 parts by weight of PP-3 were fed inthe first step and 10.4 or 31.2 parts of PP-3 were fed in the thirdstep.

The results are as shown in Table 4.

                                      TABLE 3                                     __________________________________________________________________________    Example   10 11 12 13   14   15   16                                          __________________________________________________________________________    Component (a)                                                                           100                                                                              100                                                                              100                                                                              100  100  100  100                                           Component (b) 104 104 104 104 104 104 104                                     Component (c)                                                                 PE-1 9.4 9.4 9.4 9.4 14.6 19.8 9.4                                            EP-1                                                                          Component (d)                                                                 PP-1                                                                          PP-2 21 21 21    21                                                           PP-3 10.4 10.4 10.4 21 + 10.4 21 + 10.4 21 + 31.2 10.4                        Component (e) 31 31 31    31                                                  Inorganic filler                                                              Peroxide 3.1 1 2.1 2.1 2.1 2.1 2.1                                            Cross-link auxiliary 4.7 9 10.5 4.7 4.7 4.7 4.7                               Anti-oxidant 0.2 0.2 0.2 0.2 0.2 0.2 0.2                                    __________________________________________________________________________

                                      TABLE 4                                     __________________________________________________________________________    Example         10  11  12  13 14 15 16                                       __________________________________________________________________________    Hardness, HDA, 15 sec. after                                                                  59  57  63  51 60 69 58                                         Tensile strength, kg/mm.sup.2 0.78 0.81 0.74 0.6 0.78 0.88 0.83                                                   Tensile elongation, % 470 630 510                                            670 600 520 600                            Stress at 100% elongation, kg/mm 0.42 0.32 0.37 0.28 0.38 0.44 0.35                                               Permanent set at 100% elongation, %                                          -- -- -- -- -- -- 3                        Impact resilience, % 45 43 40 58 53 49 44                                     Compression set at 70° C. 33 37 27 38 41 45 35                         Compression set at 100° C. 36 42 29 41 44 50 40                        Compression set at 120° C. 35 44 30 46 51 62 38                        Compression set at 140° C. 38 48 34 53 57 67 43                        Taper abrasion, mg/1,000 turns -- -- -- -- -- -- 200                          Spiral flow                                                                   Tear strength, kg/mm 27 30 28 -- -- -- 28                                     Resistance to oil                                                             Residual tensile strength, % 29 34 35 -- -- -- 30                             Stress at 100% elongation, kg/mm.sup.2 -- -- -- -- -- -- --                   weight change, % 27 30 28 -- -- -- 28                                         Volume change, % 29 34 35 -- -- -- 33                                         Gel ratio, %                                                                  Processability rather rather rather good good good good                        good good good                                                               Stickiness good good good good good good good                               __________________________________________________________________________

Comparative Example 1

The procedures of Example 9 were repeated with the exception thatcomponent (d), PP-3, was fed together with the other component (d),PP-1, in the first step. Nothing was fed in the third step.

The results are as shown in Table 6. From comparison between Example 9and Comparative Example 1, it is understood that particularly, thecompression set at the higher temperatures, the tear strength and theresistance to oil are excellent in the invention.

Comparative Examples to 2 to 7

The procedures of Example 9 were repeated with the materials and theamounts indicated in Table 5. That is, the amount of component (b), (c)or (e) exceeds the upper limit of the invention in Comparative Examples2 to 6. No peroxide was fed in Comparative Example 7. The results are asshown in Table 6.

                  TABLE 5                                                         ______________________________________                                        Comp. Ex.   1      2      3    4    5    6    7                               ______________________________________                                        Component (a)                                                                             100    100    100  100  100  100  100                               Component (b) 104 308 125 125 104 104 104                                     Component (c)                                                                 PE-1 4.2 9.4 104 104 25 4.2 9.4                                               EP-1 5.2                                                                      Component (d)                                                                 PP-1 10.4    10.4 10.4                                                        PP-2  21 21 21   21                                                           PP-3 21 10.4 10.4 21 10.4 21 10.4                                             Component (e) 31 31 31 31 134 134 31                                          Inorganic filler                                                              Peroxide 2.1 2.1 2.1 2.1 2.1 2.1                                              Cross-link auxiliary 4.7 4.7 4.7 4.7 4.7 4.7 4.7                              Anti-oxidant 0.2 0.2 0.2 0.2 0.2 0.2 0.2                                    ______________________________________                                    

                                      TABLE 6                                     __________________________________________________________________________    Comp. Ex.       1  2  3  4  5  6  7                                           __________________________________________________________________________    Hardness, HDA, 15 sec. after                                                                  50 37 78 95 72 90 39                                            Tensile strength, kg/mm.sup.2 0.85 -- -- -- -- -- 0.45                        Tensile elongation, % 950 -- -- -- -- -- 480                                  Stress at 100% elongation, kg/mm.sup.2 0.20 -- -- -- -- -- 0.17                                                Permanent set at 100% elongation, %                                          0.2 -- -- -- -- -- --                         Impact resilience, % 57 45 35 25 32 26 48                                     Compression set at 70° C. 36 35 45 56 42 51 30                         Compression set at 100° C. 45 47 48 58 45 52 34                        Compression set at 120° C. 58 61 50 62 51 52 34                        Compression set at 140° C. 72 67 55 68 57 58 37                        Taper abrasion, mg/1,000 turns -- -- -- -- -- -- --                           Spiral flow -- -- -- -- -- --                                                 Tear strength, kg/mm 23 45 51 49 15 12 40                                     Resistance to oil                                                             Residual tensile strength, % 40 46 35 33 16 15 64                             Stress at 100% elongation, kg/mm.sup.2 0.15 -- -- -- -- -- --                 Weight change, % 50 45 51 49 15 12 40                                         Volume change, % 53 46 35 33 16 15 64                                         Gel ratio, %                                                                  Processability good bad bad bad bad bad good                                  Stickiness good bad good good good good good                                __________________________________________________________________________

Comparative Examples 8 and 9

The procedures of Example 2 or 4 were repeated in Comparative Example 8or 9, respectively, with the exception that no peroxide was fed.

Hardnesses of the compositions obtained in Examples 2 and 4 andComparative Examples 8 and 9 were determined at room temperature, 70° C.and 110° C. to examine their heat resistance. The results are as shownin Table 7.

                  TABLE 7                                                         ______________________________________                                                   Ex. 2                                                                              Ex. 4    Comp. 8  Comp. 9                                     ______________________________________                                        Room Temperature                                                                           50     70       50     70                                           70° C. 42 60 -- --                                                    110° C. 38 50 30 40                                                  ______________________________________                                    

Incorporation of the Electron Doner Examples 17 to 30

Toluene or methanol was fed as the electron doner in the second step.Except this, the procedures of Example 1 were repeated. The materialsindicated in Tables 8 and 10 were used.

The results are as shown in Tables 9 ann 11.

Comparison Examples 10 to 17.

Comparison Examples 10 to 16 corresponds to Example 17 to 23,respectively, but toluene was not fed. The results are as sown in Table13. The number of cross-link gels was larger than 6, while no cross-linkgel was observed in Examples 17 to 23.

It should be noted that Comparative Examples 10 to 17 are comparativeonly in terms of the use of the electron doner, but are still in thescope of the invention.

In Comparative Example 17, toluene was fed in a too large amount, whichcaused stickiness.

                  TABLE 8                                                         ______________________________________                                        Example     17     18     19   20   21   22   23                              ______________________________________                                        Component (a)                                                                             100    100    100  100  100  100  100                               Component (b) 104 104 104 104 104 104 104                                     Component (c)                                                                 PE-1 4.2 9.4 14.6 19.8 25 4.2 4.2                                             EP-1      5.2 15.6                                                            Component (d)                                                                 PP-1      10.4 10.4                                                           PP-2 21 21 21 21 21                                                           PP-3 5.2 10.4 21 31 42 10.4 31                                                Component (e)      31 31                                                      Inorganic filler 31 31 31 31 31                                               Toluene 2 2 2 2 2 2 2                                                         Methanol                                                                      Peroxide 2.1 2.1 2.1 2.1 2.1 2.1 2.1                                          Cross-link auxiliary 4.7 4.7 4.7 4.7 4.7 4.7 4.7                              Anti-oxidant 0.2 0.2 0.2 0.2 0.2 0.2 0.2                                    ______________________________________                                    

                                      TABLE 9                                     __________________________________________________________________________    Example         17 18 19 20 21 22 23                                          __________________________________________________________________________    Hardness, HDA, 15 sec. after                                                                  40 49 61 69 79 51 71                                            Tensile strength, kg/mm.sup.2 0.6 0.75 0.92 1.1 1.42 0.78 1.15                Tensile elongation, % 730 740 700 670 690 710 650                             Stress at 100% elongation, kg/mm.sup.2 0.25 0.35 0.47 0.62 0.72 0.97                                          0.52                                          Permanent set at 100% elongation, % 9 9 9 5 7 9 5                             Impact resilience, % 73 71 65 60 58 65 60                                     Compression set at 70° C. 26 28 30 33 37 27 31                         Compression set at 100° C. 29 30 34 36 42 29 33                        Compression set at 120° C. 30 31 34 35 44 30 34                        Compression set at 140° C. -- -- -- -- -- -- --                        Taper abrasion, mg/1,000 turns -- -- -- -- -- -- --                           Spiral flow -- -- -- -- -- -- --                                              Tear strength, kg/mm 35 43 50 55 65 44 52                                     Resistance to oil                                                             Residual tensile strength, % 85 86 86 89 90 92 95                             Stress at 100% elongation, kg/mm.sup.2 0.19 0.3 0.49 0.56 0.68 0.34                                           0.59                                          Weight change, % 38 35 30 27 20 28 21                                         Volume change, % 35 30 24 19 14 25 19                                         Gel ratio, % 43 41 40 37 36 -- --                                             Processability good good good good good good good                             Stickiness good good good good good good good                                 Cross-link gel ⊚ ⊚ ⊚                                             ⊚ ⊚                                             ⊚ ⊚           __________________________________________________________________________

                  TABLE 10                                                        ______________________________________                                        Example     24     25     26   27   28   29   30                              ______________________________________                                        Component (a)                                                                             100    100    100  100  100  100  100                               Component (b) 104 104 104 104 104 104 104                                     Component (c)                                                                 PE-1 9.4 9.4 9.4 9.4 9.4 9.4 9.4                                              EP-1                                                                          Component (d)                                                                 PP-1                                                                          PP-2 21 21 21 21 21 21 21                                                     PP-3 10.4 10.4 10.4 10.4 10.4 10.4 10.4                                       Component (e)                                                                 Inorganic filler 31 31 31 31 31 31 31                                         Toluene 0.5 4 6 10 15                                                         Methanol      2 4                                                             Peroxide 2.1 2.1 2.1 2.1 2.1 2.1 2.1                                          Cross-link auxiliary 4.7 4.7 4.7 4.7 4.7 4.7 4.7                              Anti-oxidant 0.2 0.2 0.2 0.2 0.2 0.2 0.2                                    ______________________________________                                    

                                      TABLE 11                                    __________________________________________________________________________    Example         24 25 26 27 28 29 30                                          __________________________________________________________________________    Hardness, HDA, 15 sec. after                                                                  50 49 49 48 47 50 50                                            Tensile strength, kg/mm.sup.2 0.75 0.8 0.85 0.82 0.8 0.75 0.78                Tensile elongation, % 740 760 790 730 710 740 750                             Stress at 100% elongation, kg/mm.sup.2 0.35 0.37 0.39 0.33 0.32 0.35                                          0.34                                          Permanent set at 100% elongation, % 9 9 9 9 9 9 9                             Impact resilience, % 71 73 73 73 73 71 73                                     Compression set at 70° C. 28 28 28 28 28 28 28                         Compression set at 100° C. 30 30 30 30 30 30 30                        Compression set at 120° C. 31 31 31 31 31 31 31                        Compression set at 140° C. -- -- -- -- -- -- --                        Taper abrasion, mg/1,000 turns -- -- -- -- -- -- --                           Spiral flow -- -- -- -- -- -- --                                              Tear strength, kg/mm 43 43 43 43 43 43 43                                     Resistance to oil                                                             Residual tensile strength, % 86 86 86 82 81 86 86                             Stress at 100% elongation, kg/mm.sup.2 0.3 0.3 0.3 0.26 0.24 0.3 0.3                                           Weight change, % 35 35 35 38 40 35 35                                         Volume change, % 30 30 31 34 36 30 30                                         Gel ratio, % 43 40 38 35 33 43 41                                             Processability good good good good                                           good good good                                Stickiness good good good good good good good                                 Cross-link gel ∘ ⊚ ⊚ .circlein                                      circle. ⊚ ∘                                        ∘                               __________________________________________________________________________

                  TABLE 12                                                        ______________________________________                                        Comp. Ex.                                                                              10     11     12   13   14   15   16   17                            ______________________________________                                        Component (a)                                                                          100    100    100  100  100  100  100  100                             Component (b) 104 104 104 104 104 104 104 104                                 Component (c)                                                                 PE-1 4.2 9.4 14.6 19.8 25 4.2 4.2 9.4                                         EP-1      5.2 15.6                                                            Component (d)                                                                 PP-1      10.4 10.4                                                           PP-2 21 21 21 21 21   21                                                      PP-3 5.2 10.4 21 31 42 10.4 31 10.4                                           Component (e)      31 31                                                      Inorganic filler 31 31 31 31 31   31                                          Toluene        20                                                             Methanol                                                                      Peroxide 2.1 2.1 2.1 2.1 2.1 2.1 2.1 2.1                                      Cross-link 4.7 4.7 4.7 4.7 4.7 4.7 4.7 4.7                                    auxiliary                                                                     Anti-oxidant 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2                                ______________________________________                                    

                                      TABLE 13                                    __________________________________________________________________________    Comp. Ex.       10 11 12 13 14 15 16 17                                       __________________________________________________________________________    Hardness, HDA, 15 sec. after                                                                  41 50 62 70 79 52 71 47                                         Tensile strength, kg/mm.sup.2 0.6 0.75 0.92 1.1 1.42 0.8 1.15 0.78                                                Tensile elongation, % 730 740 700                                            670 690 690 650 660                        Stress at 100% elongation, kg/mm.sup.2 0.25 0.35 0.47 0.62 0.72 0.98                                             0.52 0.31                                  Permanent set at 100% elongation, % 9 9 9 5 7 9 5 9                           Impact resilience, % 68 69 58 55 59 58 59 71                                  Compression set at 70° C. 26 28 30 *33 37 27 31 28                     Compression set at 100° C. 29 30 34 36 42 28 33 30                     Compression set at 120° C. 30 31 34 35 44 29 34 31                     Compression set at 140° C. -- -- -- -- -- -- -- --                     Taper abrasion, mg/1,000 turns -- -- -- -- -- -- -- --                        Spiral flow -- -- -- -- -- -- -- --                                           Tear strength, kg/mm 35 43 50 55 65 41 52 43                                  Resistance to oil                                                             Residual tensile strength, % 85 86 86 89 90 96 95 79                          Stress at 100% elongation, kg/mm.sup.2 0.19 0.3 0.49 0.55 0.68 0.36                                              0.59 0.2                                   Weight change, % 38 35 30 27 20 29 21 40                                      Volume change, % 35 30 24 19 14 19 19 36                                      Gel ratio, % 45 44 42 40 38 -- -- 32                                          Processability good good good good good good good good                        Stickiness good good good good good good good bad                             Cross-link gel x x x x x Δ Δ ⊚                   __________________________________________________________________________

Incorporation of Components (e), (f) and (g) Material Used

Components (a) and (b) were same as those used in the above Examples.

PE-1 used here as component (c) was same as PE-1 used in the aboveExamples, but EP-1 here is EPR, Sumitomo Chemical Industries Co.,V-0131.

Component (d):

PP (Mitsui Petrochemical Co., CJ 700), used in the first and their stepsin Examples 31 to 35 and Comparative Examples 18 to 28; and in the thirdstep in Example 36.

TPO (Idemitsu Petrochemcial Co., E 2640), which was used in the firststep in Examples 36: low crystalline PP with a MFR of 2.5 g/10 min.

Component (e):

TPEE-1: Teijin CO., B 4010 AN, composed of 40% of a hard segment(polybutylene terephtharate) and 60% of a soft segment (polyether-estertype)

TPEE-2: Teijin Co., P 4128 AKN, composed of 40% of a hard segment(polybutyrene terephtharate) and 60% of a soft segment (polyester-estertype)

TPEE-3: Teijin Co., P 4150 AKN, composed of 75% of a hard segment(polybutyrene terephthalate) and 25% of a soft segment(polyester-polyester type).

Component (f):

Toray. Dow. Corning Co., Silicone BY 27002 (a compound of 50% by weightof dimethyl polysiloxane with a weight average molecular weight of130,000 and 50% by weight of LDPE). In Tables 14 to 18, the amount ofcomponent (f) refers to the weight parts of dimethyl polysiloxane only.

Component (g):

Toray. Dow. Corning CO., Silicone SH 200 (dimethyl polysiloxane with aweight average molecular weight of 17,000; viscosity, 1,000 cSt)

The inorganic filler,the peroxide, the crosslinking auxiliary and theanti-oxidant used here were all the same as those used in Example 1. Inthe following Examples 31 to 38 and Comparative Examples 18 to 29, theinorganic filler was used in the amount of 10 parts by weight; theperoxide, 2.6 parts by weight; the crosslinking auxiliary, 5.7 parts byweight; and the anti-oxidant, 0.2 part by weight.

A lubricant, oleyl amide (mp. 68 to 74° C., Lion Armor Co., ArmoslipCP), was used as a comparative material.

Example 31

A composition was prepared as described in Example 1.

In the first step, components (a), (b), (c), a part of component (d),components (e), (f) and (g), the inorganic filler and the anti-oxidantwere fed. The peroxide and the crosslinking auxiliary were fed in thesecond step. The remaining part of component (d) was fed in the thirdstep.

The materials and the amounts used were as indicated in Table 14. Theresults are as shown in Table 14.

Comparative Examples 18 to 21

Comparative Example 18 to 21 were carried out similarly as Example 31,but components (e), (f) and (g) were not incorporated in ComparativeExample 18, and either of component (e), (f) and (g) was not used inComparative Examples 19 to 21. The results are as shown in Table 14.Resistance to scratch is poor in these Comparative Examples.

                                      TABLE 14                                    __________________________________________________________________________                    Ex. 31                                                                            Comp. 18                                                                           Comp. 19                                                                           Comp. 20                                                                           Comp. 21                                   __________________________________________________________________________    Component (a)   100 100  100  100  100                                          Component (b) 120 120 120 120 120                                             Component (c)                                                                 PE-1 4.2 4.2 4.2 4.2 4.2                                                      EP-1                                                                          Component (d)                                                                 first step 16 16 16 16 16                                                     third step 21 21 21 21 21                                                     Component (e)                                                                 TPEE-1                                                                        TPEE-2                                                                        TPEE-3 10  10 10                                                              Component (f) 2.5   2.5 2.5                                                   Component (g) 5  5  5                                                         Comp. Component, lubricant                                                    Hardness, HDA, 15 sec. after 58 58 58 58 58                                   Tensile strength, kg/mm.sup.2 10 10 10 10 10                                  Tensile elongation, % 520 520 520 520 520                                     Stress at 100% elongation, kg/mm.sup.2 2.4 2.4 2.4 2.4 2.4                    Permanent set at 100% elongation, % 6 6 6 6 6                                 Impact resilience, % 58 58 58 58 58                                           Compression set at 70° C. 30 30 30 30 30                               Compression set at 100° C. 34 34 34 34 34                              Compression set at 120° C. 34 34 34 34 34                              Compression set at 140° C. 36 36 36 36 36                              Dynamic friction coefficient 0.35 1.1 0.65 0.84 0.73                          Load to scratch, g 380 200 270 280 240                                        Tear strength, kg/mm 29 -- -- --                                              Resistance to oil                                                             Residual tensile strength, % 88 -- -- --                                      Stress at 100% elongation, kg/mm.sup.2 2.5 -- -- --                           Weight change, % 27 -- -- --                                                  Volume change, % 24 -- -- --                                                  Gel ratio, % 39 -- -- --                                                      Processability good good good good good                                       Stickiness good good good good good                                           Bleed-out ⊚ ⊚ ⊚ .circleinci                                       rcle. ⊚                     __________________________________________________________________________

Comparative Examples 22 to 25

The amount of component (e), (f) or (g) exceeded the range of theinvention in Comparative Examples 22 to 24. The processability,stickiness or bleed-out was bad. In Comparative Example 25, components(e) and (f) were not used and, instead, the amount of component (g) wasdoubled, compared to Example 31. Then, resistance to scratch was poor.

                                      TABLE 15                                    __________________________________________________________________________                     Comp. 22                                                                           Comp. 23                                                                           Comp. 24                                                                           Comp. 25                                      __________________________________________________________________________    Component (a)    100  100  100  100                                             Component (b) 120 120 120 120                                                 Component (c)                                                                 PE-1 4.2 4.2 4.2 4.2                                                          EP-1                                                                          Component (d)                                                                 first step 16 16 16 16                                                        third step 21 21 21 21                                                        Component (e)                                                                 TPEE-1                                                                        TPEE-2                                                                        TPEE-3 40 10 10                                                               Component (f) 2.5 15 2.5                                                      Component (g) 5 5 30 10                                                       Comp. Component, lubricant                                                    Hardness, HDA, 15 sec. after 88 65 55 58                                      Tensile strength, kg/mm.sup.2 4.5 7.5 10.5 10                                 Tensile elongation, % 30 340 550 520                                          Stress at 100% elongation, kg/mm.sup.2  2.1 2.4 2.4                           Permanent set at 100% elongation, %                                           Impact resilience, % 45 58 58 58                                              Compression set at 70° C. -- -- -- 30                                  Compression set at 100° C. -- -- -- 34                                 Compression set at 120° C. 68 47 40 34                                 Compression set at 140° C. -- -- -- 36                                 Dynamic friction coefficient 0.38 0.31 0.27 0.79                              Load to scratch, g 400 380 360 250                                            Tear strength, kg/mm -- -- -- --                                              Resistance to oil                                                             Residual tensile strength, % -- -- -- --                                      Stress at 100% elongation, kg/mm.sup.2 -- -- -- --                            Weight change, % -- -- -- --                                                  Volume change, % -- -- -- --                                                  Gel ratio, % -- -- -- --                                                      Processability bad good good good                                             Stickiness good good bad good                                                 Bleed-out ⊚ Δ x ⊚                       __________________________________________________________________________

Comparative Examples 26 to 28

In Comparative Example 26, use was made of the lubricant which isconventionally used to obtain surface lubricity of a molded article. Theresults are as shown in Table 16. The lubricant came up to the surface.Thus, the bleed-out property was bad. In Comparative Examples 27 and 28,one or two of components (e), (f) and (g) of the invention were not usedand, instead, the lubricant was used. The bleed-out property was bad.

                  TABLE 16                                                        ______________________________________                                                        Comp. 26                                                                             Comp. 27 Comp. 28                                      ______________________________________                                        Component (a)     100      100      100                                         Component (b) 120 120 120                                                     Component (c)                                                                 PE-1 4.2 4.2 4.2                                                              EP-1                                                                          Component (d)                                                                 first step 16 16 16                                                           third step 21 21 21                                                           Component (e)                                                                 TPEE-1                                                                        TPEE-2                                                                        TPEE-3  10                                                                    Component (f)  2.5                                                            Component (g)   5                                                             Comp. Component, lubricant 1.5 1.5 1.5                                        Hardness, HDA, 15 sec. after 58 58 58                                         Tensile strenqth, kg/mm.sup.2 10 10 10                                        Tensile elonqation, % 520 520 520                                             Stress at 100% elongation, kg/mm.sup. 2.4 2.4 2.4                             Permanent set at 100% elongation, % 6 6 6                                     Impact resilience, 58 58 58                                                   Compression set at 70° C. 30 30 30                                     Compression set at 100° C. 34 34 34                                    Compression set at 120° C. 34 34 34                                    Compression set at 140° C. 36 36 36                                    Dynamic friction coefficient 0.56 0.48 0.51                                   Load to scratch, g 260 300 270                                                Tear strenqth, kg/mm -- -- --                                                 Resistance to oil                                                             Residual tensile strength, % -- -- --                                         Stress at 100% elongation, kg/mm.sup.2 -- -- --                               Weight change, % -- -- --                                                     Volume change, % -- -- --                                                     Gel ratio, % -- -- --                                                         Processability good good good                                                 Stickiness good good good                                                     Bleed-out Δ Δ Δ                                           ______________________________________                                    

Examples 32 to 36

In Examples 32 to 34, a different type of component (e) or (c) from thatused in Example 31 was used. As seen from Table 17, the satisfactoryresults were attained. In Example 35, the amounts of component (d) forthe first and third steps and the amount of component (b) were changedfrom those of Example 31. The good results were attained.

In Example 36, a different type of component (d) was used in the firststep, as mentioned above, and the amounts of component (d) in the firstand third steps were changed from those of Example 31. The hardness wasso small as 39A and, nevertheless, the rubber properties at the highertemperatures, the resistance to oil and the processability wereexcellent, and the other properties were also good.

                                      TABLE 17                                    __________________________________________________________________________                     Ex. 32                                                                            Ex. 33                                                                            Ex. 34                                                                            Ex. 35                                                                            Ex. 36                                       __________________________________________________________________________    Component (a)    100 100 100 100 100                                            Component (b) 120 120 120 42 120                                              Component (c)                                                                 PE-1 4.2 4.2 1.2 4.2 4.2                                                      EP-1   4.2                                                                    Component (d)                                                                 first step 16 16 16 26 21                                                     third step 21 21 21 13 10                                                     Component (e)                                                                 TPEE-1 10                                                                     TPEE-2  10                                                                    TPEE-3   10 10 10                                                             Component (f) 2.5 2.5 2.5 2.5 2.5                                             Component (g) 5 5 5 5                                                         Comp. Exonent, lubricant                                                      Hardness, HDA, 15 sec. after 58 58 58 80 39                                   Tensile strength, kg/mm 10 10 10 18 6.5                                       Tensile elongation, % 520 520 520 500 470                                     Stress at 100% elongation, kg/mm.sup.2 2.4 2.4 2.4 4.7 1.4                    Permanent set at 100% elongation, % 6 6 6 6 6                                 Impact resilience, % 58 58 58 47 67                                           Compression set at 70° C. 30 30 30 37 26                               Compression set at 100° C. 34 34 34 42 29                              Compression set at 120° C. 34 34 34 44 30                              Compression set-at 140° C. 36 36 36 49 32                              Dynamic friction coefficient 0.37 0.36 0.35 0.32 0.4                          Load to scratch, g 330 310 380 350 390                                        Tear strength, kg/mm -- -- -- 40 17                                           Resistance to oil                                                             Residual tensile strength, % -- -- -- 97 85                                   Stress at 100% elongation, kg/mm.sup.2 -- -- -- 4.7 1.5                       Weight change, % -- -- -- 29 35                                               Volume change, % -- -- -- 26 32                                               Gel ratio, % -- -- -- 37 42                                                   Processability good good good good good                                       Stickiness good good good good good                                           Bleed-out ⊚ ⊚ ⊚ .circleinci                                     rcle. ⊚                       __________________________________________________________________________

Examples 37 and 38 and Comparative Example 29

As component (f), use was made of the following fluorized oligomer aloneor together with the aforesaid silicone, BY 27002.

Fluorized oligomer, DIK CO., Megafac F-178 RM (olefinic oligomer havinga perfluoroalkyl group, weight average molecular weight 6,500)

As component (d), the aforesaid CJ 700 was used.

The results are as shown in Table 18.

                  TABLE 18                                                        ______________________________________                                                         Ex. 37                                                                              Ex. 38   Comp. 29                                      ______________________________________                                        Component (a)      100     100      100                                         Component (b) 120 120 120                                                     Component (c)                                                                 PE-1 4.2 4.2 4.2                                                              EP-1                                                                          Component (d)                                                                 first step 16 16 16                                                           third step 21 21 21                                                           Component (e)                                                                 TPEE-3 10 10 10                                                               Component (f)                                                                 fluorized oligomer 0.5 0.3 2                                                  silicone -- 3 --                                                              Component (g) 5 5 --                                                          Comp. Component, lubricant                                                    Hardness, HDA, 15 sec. after 58 58 58                                         Tensile strength, kg/mm.sup.2 10 10 10                                        Tensile elongation, % 520 520 520                                             Stress at 100% elongation, kg/mm.sup.2 2.4 2.4 2.4                            Permanent set at 100% elongation, % 6 6 6                                     Impact resilience, % 58 58 58                                                 Compression set at 70° C. 30 30 30                                     Compression set at 100° C. 34 34 34                                    Compression set at 120° C. 34 34 34                                    Compression set at 140° C. 36 36 36                                    Dynamic friction coefficient 0.4 0.35 0.85                                    Load to scratch, g 380 400 280                                                Tear strength, kg/mm 29 29 29                                                 Resistance to oil                                                             Residual tensile strength, % 88 88 88                                         Stress at 100% elongation, kg/mm.sup.2 2.5 2.5 2.5                            Weight change, % 27 27 27                                                     Volume change, % 24 24 24                                                     Gel ratio, % 39 39 39                                                         Processability                                                                Stickiness good good good                                                     Bleed-out ⊚ ⊚ ⊚                ______________________________________                                    

Incorporation of the Hydrogenated Petroleum Resin

Components (a), (b) and (c) used below were same as those used inExample 1.

Regarding component (d) , PP-1 and PP-3 were same as those used inExample 1, and PP-2 was TPO (Idemitsu Petrochemical Co., E 2640) used inExample 31.

The hydrogenated petroleum resin was Aimarb P-140 (IdemitsuPetrochemical Co., hydrogenated C₅ -aromatic type copolymeric resin)

The inorganic filler, the peroxide, the crosslinking auxiliary and theanti-oxidant used here were all same as those used in Example 1.

Examples 39 to 46

Compositions were prepared as described in Example 1.

When the hydrogenated petroleum resin was incorporated according to theinvention, the whole amount of component (d) may be subjected to theheat treatment in the presence of an organic peroxide, or a part ofcomponent (d) may be blended later in the third step.

In Examples 39 to 43 and 45 to 46, the whole amount of component (d) wasfed in the first step. Nothing was fed in the third step, but thecomposition was put through the third step similarly.

In Example 44, component (d), PP-2, was fed in the first step and theremaining component (d), PP-3, was fed in the third step.

The amounts used were as shown in Table 19. The results are as shown inTable 20.

                                      TABLE 19                                    __________________________________________________________________________                    Ex. 39                                                                            Ex. 40                                                                            Ex. 41                                                                            Ex. 42                                                                            Ex. 43                                                                            Ex. 44                                                                            Ex. 45                                                                            Ex. 46                            __________________________________________________________________________    Component (a)   100 100 100 100 100 100 100 100                                 Component (b) 156 156 156 125 230 156 188 188                                 Component (c)                                                                 PE-1 4.2 4.2 4.2 4.2 4.2 4.2 4.2 4.2                                          EP-1                                                                          Component (d)                                                                 PP-1                                                                          PP-2 21 21 21 21 21 21 21 21                                                  PP-3      15                                                                  Hydrogenated Petro. Resin 21 42 100 42 42 42 21 42                            Inorganic filler 10 10 10 10 10 10 10 10                                      Peroxide 2.6 2.6 2.6 2.6 2.6 2.6 2.6 2.6                                      Crosslinking Auxiliary 5.7 5.7 5.7 5.7 5.7 5.7 5.7 5.7                        Anti-oxidant 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2                                __________________________________________________________________________

                                      TABLE 20                                    __________________________________________________________________________                    Ex. 39                                                                            Ex. 40                                                                            Ex. 41                                                                            Ex. 42                                                                            Ex. 43                                                                            Ex. 44                                                                            Ex. 45                                                                            Ex. 46                            __________________________________________________________________________    Hardness, HDA, 15 sec. after                                                                  21  19  13  30  13  30  17  15                                  Hardness, Asker C 43 40 31 53 30 53 37 33                                     Tensile strength, kg/mm.sup.2 3.4 3.5 1.0 7.0 0.9 4.8 2.7 3.8                 Tensile elongation, % 620 640 560 550 540 650 720 800                         Stress at 100% elongation, kg/mm.sup.2 0.7 0.7 0.5 1.0 0.3 1.1 0.5 0.5                                                   Permanent set at 100%                                                        elongation, % 6 6 6 7 6 8 6 6       Impact resilience, % 73 73 71 65 73 71 73 73                                  Compression set at 70° C. 29 30 38 33 32 29 28 30                      Compression set at 100° C. 32 35 51 39 38 31 34 36                     Compression set at 120° C. 40 46 56 46 46 42 48 51                     Compression set at 140° C. 51 56 62 50 53 49 57 65                     Dynamic friction coefficient 0.86 0.87    0.76 0.87 0.86                      Tear strength, kg/mm 12 10    15 10 12                                        Resistance to oil                                                             Residual Tensile strength, % 83 82    85 82 81                                Stress at 100% elongation, kg/mm.sup.2                                        Weight change, % 37 37    35 39 39                                            Volume change, % 34 34    33 36 36                                            Gel ratio, % 43 43    42 40 37                                                Processability good good good good good good good good                        Stickiness good good good good good good good good                            Bleed-out ⊚ ⊚ ⊚ .circleinci                                                rcle. ⊚                                                        ⊚ .circleincirc                                                le. ⊚              __________________________________________________________________________

Examples 47 to 55

PP-1 or PP-2 as component (d) was fed in the first step, and PP-3 ascomponent (d) was fed in the third step in the amount indicated in Table21.

In Example 54, PE-1 as component (c) was fed in the first step and EP-1was fed in the second step. In Example 55, each 2.1 parts of PE-1 wasfed both in the first and seconds steps.

The results are as shown Table 22.

                                      TABLE 21                                    __________________________________________________________________________                Ex. 47                                                                            Ex. 48                                                                            Ex. 49                                                                            Ex. 50                                                                            Ex. 51                                                                            Ex. 52                                                                            Ex. 53                                                                            Ex. 54                                                                            Ex. 55                            __________________________________________________________________________    Component (a)                                                                             100 100 100 100 100 100 100 100 100                                 Component (b) 188 188 146 230 188 188 188 18.8 188                            Component (c)                                                                 PE-1 4.2 4.2 4.2 4.2 4.2 4.2 4.2 2.1 2.1 + 2.1                                EP-1        2.1                                                               Component (d)                                                                 PP-1  10 10 10                                                                PP-2 21 0 0 0 60 21 21 21 21                                                  PP-3 25 10 10 10 10 25 25 15 15                                               Hydrogenated Petro. Resin 42 42 42 42 42 42 42 42 42                          Inorganic filler 10 10 10 10 10 10 10 10 10                                   Peroxide 2.6 2.6 2.6 2.6 2.6 2 3 2.6 2.6                                      Crosslinking Auxiliary 5.7 5.7 5.7 5.7 5.7 4.4 6.6 5.7 5.7                    Anti-oxidant 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2                            __________________________________________________________________________

                                      TABLE 22                                    __________________________________________________________________________                    Ex. 47                                                                            Ex. 48                                                                            Ex. 49                                                                            Ex. 50                                                                            Ex. 51                                                                            Ex. 52                                                                            Ex. 53                                                                            Ex. 54                                                                            Ex. 55                        __________________________________________________________________________    Hardness, HDA, 15 sec. after                                                                  30  30  30  29  31  30  29  30  30                              Hardness, Asker C 53 53 54 50 54 53 51 53 53                                  Tensile strength, kg/mm.sup.2 4.1 7.2 6.2 5.2 6.5 4.1 3.9 4.8 4.8                                                            Tensile elongation, %                                                        580 620 550 560 610 560                                                       510 650 650                     Stress at 100% elongation, kg/mm.sup.2 0.8 1.8 1.5 1.4 1.6 0.9 1.1 1.1                                                      1.1                             Permanent set at 100% elongation, % 7 8 6 6 8 6 6 8 8                         Impact resilience, % 71 71 67 69 61 63 65 71 71                               Compression set at 70° C. 31 31 30 30 33 29 28 29 29                   Compression set at 100° C. 33 33 35 36 38 33 31 31 31                  Compression set at 120° C. 47 45 39 45 45 38 35 42 42                  Compression set at 140° C. 52 51 46 54 57 41 39 49 49                  Dynamic friction coefficient 0.79 0.86   0.8 0.87 0.86 0.76 0.76                                                             Tear strength, kg/mm 15                                                      20   32 32 33 15 15                                                            Resistance to oil                                                             Residual tensile                                                             strength, % 84 84   75 87                                                      85 85                          Stress at 100% elongation, kg/mm.sup.2                                        Weight change, % 36 36   35 37 36 35 35                                       Volume change, % 34 34   33 34 34 33 33                                       Gel ratio, % 37 39   37 37 38 42 45                                           Processability good good good rather good good good good good                     good                                                                      Stickiness good good good rather good good good good good                         good                                                                      Bleed-out ⊚ ⊚ ⊚ .smallcircl                                                    e. ⊚                                                           ∘ .circleincir                                                    cle. ⊚                                                         ⊚              __________________________________________________________________________

Comparison Examples 30 to 35

Using the materials indicated in Table 23, compositions were prepared asin Example 39. In Comparison Example 30, no hydrogenated petroleum resinwas used. In Comparison Examples 31 to 35, the amount of component (b)or the hydrogenated petroleum resin was too small or too large. PP-2 ascomponent (d) was fed in the first step. In Comparison Example 35, PP-3was further fed in the third step.

The results are as shown in Table 24.

                                      TABLE 23                                    __________________________________________________________________________              Comp. 30                                                                           Comp. 31                                                                           Comp. 32                                                                           Comp. 33                                                                           Comp. 34                                                                           Comp. 35                                   __________________________________________________________________________    Component (a)                                                                           100  100  100  100  100  100                                          Component (b) 156 156 156 15 350 156                                          Component (c)                                                                 PE-1 4.2 4.2 4.2 4.2 4.2 4.2                                                  EP-1                                                                          Component (d)                                                                 PP-1                                                                          PP-2 21 21 21 21 21 21                                                        PP-3 15                                                                       Hydrogenated  5 126 42 42 126                                                 Petro. Resin                                                                  Inorganic filler 10 10 10 10 10 10                                            Peroxide 2.6 2.6 2.6 2.6 2.6 2.6                                              Crosslinking Auxiliary 5.7 5.7 5.7 5.7 5.7 5.7                                Anti-oxidant 0.2 0.2 0.2 0.2 0.2 0.2                                        __________________________________________________________________________

                                      TABLE 24                                    __________________________________________________________________________                    Comp. 30                                                                           Comp. 31                                                                           Comp. 32                                                                           Comp. 33                                                                           Comp. 34                                                                           Comp. 35                             __________________________________________________________________________    Hardness, HDA, 15 sec. after                                                                  23   22   13   55   10   26                                     Hardness, Asker C 46 44 31 72 26 48                                           Tensile strength, kg/mm.sup.2 2.8 2.7 1.1 7.5 0.6 4.0                         Tensile elongation, % 590 610 560 520 380 480                                 Stress at 100% elongation, kg/mm.sup.2 0.5 0.5 0.4 1.6 0.1 0.4                Permanent set at 100% elongation, % 6 6 6 7 5 9                               Impact resilience, % 73 73 73 65 73 69                                        Compression set at 70° C. 28 30 34 32 30 32                            Compression set at 100° C. 30 36 43 40 42 35                           Compression set at 120° C. 36 40 56 45 56 51                           Compression set at 140° C. 45 51 65 53 68 64                           Dynamic friction coefficient 0.87     0.85                                    Tear strength, kg/mm 10                                                       Resistance to oil                                                             Residual tensile strength, % 81     80                                        Stress at 100% elongation, kg/mm.sup.2 0.19                                   Weight change, % 38     37                                                    Volume change, % 35     34                                                    Gel ratio, % 45     37                                                        Processability bad bad good bad bad good                                      Stickiness good good bad good bad bad                                         Bleed-out ⊚ ⊚ ⊚ .circleinci                                             rcle. x ⊚             __________________________________________________________________________

Comparison Examples 36 to 41

Using the materials indicated in Table 25, compositions were prepared asin Example 39.

PP-1 or PP-2 was fed in the first step, and PP-3 was fed in the thirdstep.

The results are as shown in Table 26.

                                      TABLE 25                                    __________________________________________________________________________              Comp. 36                                                                           Comp. 37                                                                           Comp. 38                                                                           Comp. 39                                                                           Comp. 40                                                                           Comp. 41                                   __________________________________________________________________________    Component (a)                                                                           100  100  100  100  100  100                                          Component (b) 188 188 188 188 146 230                                         Component (c)                                                                 PE-1 4.2 4.2 4.2 4.2 4.2 4.2                                                  EP-1                                                                          Component (d)                                                                 PP-1    10 10 10                                                              PP-2 21 21 21 0 0 0                                                           PP-3   25 10 10 10                                                            Hydrogenated  126 126                                                         Petro. Resin                                                                  Inorganic filler 10 10 10 10 10 10                                            Peroxide 2.6 2.6 2.6 2.6 2.6 2.6                                              Crosslinking Auxiliary 5.7 5.7 5.7 5.7 5.7 5.7                                Anti-oxidant 0.2 0.2 0.2 0.2 0.2 0.2                                        __________________________________________________________________________

                                      TABLE 26                                    __________________________________________________________________________                    Comp. 36                                                                           Comp. 37                                                                           Comp. 38                                                                           Comp. 39                                                                           Comp. 40                                                                           Comp. 41                             __________________________________________________________________________    Hardness, HDA, 15 sec. after                                                                  19   11   28   34   40   33                                     Hardness, Asker C 41 29 50 55 60 55                                           Tensile strength, kg/mm.sup.2 2.5 0.9 3.5 7.5 6.8 5.4                         Tensile elongation, % 620 580 560 630 520 540                                 Stress at 100% elongation, kg/mm.sup.2 0.4 0.2 0.4 1.8 1.6 1.4                Permanent set at 100% elongation, % 6 5 8 6 7 6                               Impact resilience, % 73 73 71 69 65 67                                        Compression set at 70° C. 27 32 33 32 32 34                            Compression set at 100° C. 32 45 38 33 36 41                           Compression set at 120° C. 41 58 56 46 41 52                           Compression set at 140° C. 49 68 63 53 49 62                           Dynamic friction coefficient 0.88  0.82  0.88 0.87                            Tear strength, kg/mm 8  9  25 18                                              Resistance to oil                                                             Residual tensile strength, % 80  82  81 76                                    Stress at 100% elongation, kg/mm.sup.2                                        Weight change, % 39  40  35 42                                                Voiume change, % 36  37  33 39                                                Gel ratio, % 39  33  43 36                                                    Processability bad good good good good good                                   Stickiness good bad bad good good bad                                         Bleed-out ⊚ x ⊚ ⊚ .circlein                                             circle. Δ                      __________________________________________________________________________

We claim:
 1. A thermoplastic elastomeric resin compositioncomprising:(a) 100 parts by weight of a block copolymer consisting of atleast two polymeric blocks (A) composed mainly of a vinyl aromaticcompound and at least one polymeric block (B) composed mainly of aconjugated diene compound, or a hydrogenated block copolymer obtained byhydrogenating said block copolymer, (b) 20 to 300 parts by weight of anon-aromatic softening agent for rubber, (c) 1 to 100 parts by weight ofa peroxide-crosslinking olefinic resin or a copolymeric rubbercontaining said resin, and (d) 10 to 150 parts by weight of aperoxide-decomposition olefinic resin or a copolymer containing saidresin,characterized in that the composition further comprises (e) 1 to30 parts by weight of a polyester thermoplastic elastomer, (f) 0.5 to 10parts by weight of a silicone having a weight average molecular weightof at least 70,000 or 0.1 to 3 parts by weight of a compound having aperfluoroalkyl group, and (g) 1 to 20 parts by weight of a straightsilicone oil having a weight average molecular weight of at most 50,000,andthat the composition is one which is subjected to cross-linkingtreatment in the presence of an organic peroxide.
 2. The thermoplasticelastomeric resin composition as described in claim 1, whereincomponents (a), (b), a part of (c), at least a part of (d), (e), (f) and(g) are subjected to the cross-linking treatment, and the remainingparts of (c) and, if any, (d) are then blended.
 3. The thermoplasticelastomeric resin composition as described in claim 1, wherein thecomposition further comprises 100 parts by weight or less of aninorganic filler.
 4. The thermoplastic elastomeric resin composition asdescribed in claim 1, wherein the composition further comprises 0.1 to10 parts by weight of an ethylenically unsaturated monomer as across-linking auxiliary.
 5. A thermoplastic elastomeric resincomposition comprising:(a) 100 parts by weight of a block copolymerconsisting of at least two polymeric blocks (A) composed mainly of avinyl aromatic compound and at least one polymeric block (B) composedmainly of a conjugated diene compound, or a hydrogenated block copolymerobtained by hydrogenating said block copolymer, (b) 20 to 300 parts byweight of a non-aromatic softening agent for rubber, (c) 1 to 100 partsby weight of a peroxide-crosslinking olefinic resin or a copolymericrubber containing said resin, and (d) 10 to 150 parts by weight of aperoxide-decomposition olefinic resin or a copolymer containing saidresin,characterized in that the composition further comprises (h) 10 to100 parts by weight of a hydrogenated petroleum resin, andthat thecomposition is one which is subjected to cross-linking treatment in thepresence of an organic peroxide.
 6. The thermoplastic elastomeric resincomposition as described in claim 5, wherein components (a), (b), a partof (c), at least a part of (d) and (h) are subjected to thecross-linking treatment, and the remaining parts of (c) and, if any, (d)are then blended.
 7. The thermoplastic elastomeric resin composition asdescribed in claim 5, wherein the composition further comprises 100parts by weight or less of an inorganic filler.
 8. The thermoplasticelastomeric resin composition as described in claim 5, wherein thecomposition further comprises 0.1 to 10 parts by weight of anethylenically unsaturated monomer as a crosslinking auxiliary.